Catalytic interplay of metal ions (Cu2+, Ni2+, and Fe2+) in MFe2O4inverse spinel catalysts for enhancing the activity and selectivity during selective transfer hydrogenation of furfural into 2-methylfuranElectronic supplementary information (ESI) available: Experimental procedures, detailed synthesis and characterization of catalysts, catalytic procedures, DFT calculation procedure, textural properties, FE-SEM images, and recycling data are provided. See DOI: https://doi.org/10.1039/d2cy00970f

2-Methylfuran obtained viathe hydrogenation of furfural is an important biomass-derived liquid fuel. However, the large-scale production of 2-methylfuran from furfural requires cost-effective, active, and selective heterogeneous catalysts. Herein, we have performed experimental and DFT investigations on MFe2O4(M = Cu2+, Ni2+, and Fe2+) inverse spinel catalysts to selectively hydrogenate furfural into 2-methylfuran viatransfer hydrogenation, and to determine the nature of active sites. CuFe2O4afforded 99.4% furfural conversion and 97.6% 2-methylfuran selectivity at 200 °C in 1.5 h. In contrast, NiFe2O4and Fe3O4catalysts afforded furfuryl alcohol as a major product. The comprehensive characterization of the catalysts revealed that the acidity of these inverse spinel catalysts originates from the Lewis acid sites. Further, the strength of Lewis acid sites and the associated catalytic activity trend directly correlate with the binding energy of Fen+ions in MFe2O4catalysts. DFT calculations revealed the energetically favorable interactions of furfural and furfural alcohol with the Fe3+sites of Fe3O4and Fe sites (most likely Fe3+) of CuFe2O4and NiFe2O4catalysts, whereas Cu2+and Ni2+sites present in CuFe2O4and NiFe2O4catalysts have stronger interactions with the isopropanol molecule. Hence, it is proposed that the Fe3+sites present in CuFe2O4are the active Lewis acid centers to selectively convert furfural into 2-methylfuran viatransfer hydrogenation. Literature reports on the metal oxide catalyzed transfer hydrogenation of furfural into 2-methylfuran are rare. The present findings on the elucidation of the active sites of cost-effective, recyclable mixed metal oxide catalysts for the selective transfer hydrogenation of furfural into 2-methylfuran using isopropanol are attractive from the green chemistry perspective, and therefore extremely important for the academic catalysis community and to industrialists.